Azo compounds and process for dyeing therewith



Patented Feb. 8, 1938 UNITED s'raxnzs PATENT OFFICE A AZO COMPOUNDS AND PROCESS FOR DYE- ING THEREWITH James G. McNally and Joseph B. Dickey, Rochester, N. Y assignors, by mesne assignments, to Eastman Kodak Company, Jersey City, N. 1.,

a corporation of New Jersey No Drawing. Application May a, 1930, Serial No. 78,170

. 14 Claims- This invention relates to new arylazo compositions More particularly it relates 'to water soluble aryl azo compounds suitablefor-the coloration of organic derivatives of cellulose, silk 5. or wool, by dyeing, printing or stenciling, as well as for the union dyeing of materials containing these substances. Theinvention' includes the new aryl azo compounds, the process for their manufacture, the process of dyeing with the 1o watersoluble azo compounds of the invention and ized by an 'indliterent amnity for the usual cot-.-

-ton or wool dyes, especially the ordinary water soluble dyes. Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed organic acid esters of cellulose, such as cellulose acetate, cellulose formate, cellulose propionate or cellulose ,butyrate, and the hydrolyzed-as well as the unhydrolyzed mixed organic acid esters of cellulose, such as cellulose acetate-propionate, cellulosev acetate-butyrate and the cellulose ethers, such as methyl cellulose, ethyl cellulose or benzyl cellulose.

' The term cellulose acetate" as used herein is intended to include such acetylated. cellulose products as are characterized by an indifferent '35" aiiinity for the usual cotton or wool-dyes. es-

pecially the ordinary water soluble dyes. More. particularly, it refers to acetate silk made from a cellulose acetate product having an acetylation value higher than cellulose diacetate andlower 40 than cellulose triacetate but, as justsnoted, the

term cellulose acetate is not restricted to this more limited meaning. l

The aryl azo compounds of our invention can be preparedby coupling nuclear non-sulfonated.

cyclic group and Z represents hydrogen, an alkali-forming metal or an ammonium radical.

Referring more-particularly to the constituents which goto form the compounds having the general formula above given, A represents an al- 5 hvlene group which advantageously can be an ethylene, a methylethylene, a propylene or a butylene group, It represents a nuclear non-sulfonated aryl group. advantageously of the hen-- zene or naphthalene series, such as phenyl, chlo- 10 rophenyl, hydroxyphenyl, nitrophenyi, alkoxyj phenyl, diphenyl, alkoxytolyl, naphthyl or nitronaphthyl. X represents a hydrogen atom or an alkyl group which can advantageously be a methyl, an alkoxymethyl, ethyl, propyl, butyl, 15 hexyl, a sulfonatedethyl group, such as:

or a higher albl sulfonated group such as:

cm-cm-cn=-cm-so=on was-summons.

x can also be a nuclear non-sulfonated aryl group preferably of the benzene or naphthalene 25 series, such as phenyl, chlorophenyl, nitrophenyi, alkoxyphenyl, naphthyl or nitronaphthyl. Likewise x can be a cycloal yl group, such as cyclohexyl or tetrahydronaphthyl or a heterocyclic groupsuch as tetrahydroi'uryl. Z can be a hy- 3o drogen atom, an alkali-forming metal, such as sodium, potassium or calcium, an ammonium radical derived from ammoniaor .a substituted ammonia (i.e. a basic amine), such as methylamine, dimethyiamine, trimethylamine, ethyl- 35 amine, fl-hydroxyethylamine, di-p-hydroxyethylamine, butylamine, benzyl amine,- pyridine or the like, or a quaternary ammonium radical such as tetramethyl ammonium tetraethylammonium or thelike.

Thecompounds of our invention can be pre pared by diazotlzing a nuclear non-suli'onated aromatic amine in an acid medium and coupling it with a compound of the general formula above described. Their probable structural formula is as follows:

l soz R'N=NR-N x I wherein R represents a nuclear non-sulfonated aryl nucleus which may be substituted and R, A, x and Z have the meaning previously assigned to them.

The compounds of our invention are characstable to heat and may be subjected to comparatively high temperatures without undergoing decomposition. Because of their solubility in water they may be used for dyeing without the necessity of employing dispersing agents. As a general rule, it may he stated that their solubility in water decreases with increase in the number of carbon atoms in the allrylene group attached to the sulphonic acid group. Similarly,

as a general rule, the solubility in water decreases with increase in the molecular weight of the substituent represented by X.

We are aware that it is known from English Patent No. 11,343 of 1899 to prepare compounds having the general formula:

RN=NR'N-CH=.S03H f wherein R and R, respectively, indicate aryl groups or nuclei, by combination of diazo compounds with the methyl-omega-sulphonic acids derived from primary amines; that is, amines having a hydrogen atom replaced by the methylv omega-sulphonlc acid. Similarlywe are aware from the United States Patents Nos. 1,483,797 and 1,483,798 to Green and Saunders that am compounds having omega-suiphonic acids other than methyl-omega-sulphonic acid are known and are stated to be of use for dyeing acetyl cellulose.

The azo-sulphonic acid compounds of our invention are distinguished from the omega-sulphonic acid compounds disclosed by the prior art in that, as stated in the patents to Green and Saunders, the omega-sulphonic acid groups split off during the dyeing operation, whereas in the 9.20 compounds of our invention the sulphonic acid group' does'not split off during the dyeing operation. Dissociation of the omega-sulphonic acids is stated to occur in "hot aqueous solution especially if it be slightly acid or slightly alkaline. Such dissociation does not occur in the case of the am compounds of our invention. Again, the azo compounds of this invention are further distinguished in that they possess high stability to heat, whereas the corresponding azo compounds having omega-sulphonic acid groups, are usually relatively unstable to heat.

The new coupling component of our invention A-S0;Z

n-rr

is prepared by heating an arylamine having the stmcturalformula has the meaning previously given it, with B-SOsZ where B represents a halogen substituted alkylene group other than methylene and in which Z represents hydrogen, an alkali-forming metal or an ammonium radical. Thus, for

example, the coupling component methyl-fl-sulfoethyl aniline can be prepared-by heating one mole of methyl aniline and one mole of p-bromoeghane sulfonate at a temperature of about 1 0 C.

hydrochloric acid.

Our invention will be more fully understood by reference to the following examples, in which the quantities are stated in parts by weight:

Example 1 taining a temperature of 0 -5 C. Sodium acetate is then added until the solution is no longer acid to Congo red paper and the axe compound of p-bromo-aniline and methyl-p-sulfoethylaniline precipitated as the sodium salt by the addition of sodium chloride, filtered and dried.

Example 2 27.3 parts of p-smfoethyla-naphthylamine are dissolved in a minimum amount of acetic acid and the diazonium salt, prepared as described in Example 1, added. Ethanolamine is then added until the resulting solution is no longer acid to Congo red paper. After coupling is complete, the resulting azo compound is precipitated as the ethanolamine salt by the addition of sodium chloride, filtered and dried. By the substitution of sodium acetate for ethanolamine, the sodium salt of the azo compound can be obtained.

Example 3 16.8 parts of 2-methoxy-4-nitroaniline are dissolved by warming in 200 parts of water containing about 35 parts of 36% hydrochloric acid and diazotized in the usual manner by adding 6.9 parts of sodium nitrite dissolved in a small amount of water.

23.7 parts of methyl-p-sulfoethylaniline are dissolvedin a minimum quantity of acetic acid and the diazonium salt added. The resulting solution is then made neutral to Congo red paper by the addition of pyridine. When coupling is complete the pyridine salt of the resulting azo compound is precipitated with salt, flltered and dried. The sodium salt of the azo compound can be pregjared by substituting sodium acetate for pyri- Example 4 of p-sulfoethyl-m-naphthylamine are dissolved in acetic acid, preferably the minimum amount, and the diazonium salt, prepared as described in Example 3, is added. The solution is then made neutral to Congo red paper with sodium acetate, and after reaction is complete the azo compound of 2-methoxy-4-nitroaniline and fl-sulfoethyl-a-naphthylamine is precipitated as the sodium salt with sodium chloride, filtered and dried.

Example 5 A. 7.6 parts of powdered sodium nitrite are dissolved in 97.5 parts of cold 100% sulfuric acid, and after the addition, the solution is warmed to not over C. after which it is cooled to Ill-15 C.

B. 18.3 parts of 2,4-dinitroaniline are dissolved in 231 parts of hot glacial acetic acid, and the resulting solution cooled as rapidly as possible to room temperature.

The mixture prepared in B is added to the solution prepared in A over av period of 30-45 minutes, while stirring, and maintaining a temperature of 10-i5C. The resulting solution is stirred for about an additional 30 minutes, and one part of urea is added to remove excess nitrous acid.

23.7 parts. of methyl-msulioethyl-a-naphthylamine are dissolved in a minimum amount of acetic acid, and coupled in the usual manner with the diazo solution prepared above. After coupling is complete the resulting azo compound is precipitated with salt, filtered and dried.

Example 6 bonate.'

Example 7 7.2 parts of sodium nitrite are slowly added to 114 parts of cold sulfuric acid. The resultingsolution is cooled and 22.8 parts of 2,4,6- trinitroaniline in finely-powdered form are added. The suspension is cooled and stirred for one hour, and then at room temperature for 10-12 hours until it no longer shows an excess of nitrous acid when tested with starch potassium iodide paper.

The diazo salt thus prepared is added to 23.7

' parts of methyl-19+sulfoethyianiline, dissolved in a minimum amount of acetic acid and-coupling is effected in the usual manner. When coupling is complete, the mixture is poured into water, made neutral to Congo red paper with sodium acetate, after which the azo compound is precipitated with sodium. chloride, filtered and dried.

Example 8 13.5 parts of p-aminoacetophenone are dissolved in parts of water containing about 30 parts of 36% hydrochloric acid and diazotized in the usual manner by the addition oi. 6.9 parts of sodium nitrite.

32.3 parts of ammoniumsuli'opropylbutylmetachloroaniline are dissolved in water. Preferably a minimum amount of water is used. The resulting solution is then iced or otherwise cooled to a temperature of about 0 C. and the diazo solution prepared above is added slowly with stirring. Concurrently with the addition of the diazo solution there is added a water solution of sodium acetate, sodium carbonate or sodium bicarbonate in amount suflicient to keep the mixture just neutral to Congo red paper. When coupling is complete, the azo compound is precipitated by addition of salt, or in any suitable manner, filtered and dried.

Example 9 A; 7.6 parts of sodium nitrite are dissolved in 97.5 parts oi. cold 100% sulfuric acid and after the addition, the solution is warmed to not over 70 C. and then cooled to 10-15 C.

B. 26.2 parts of 2,4-dinitro-6-bromoaniline are dissolved in 241 parts of hot glacial acetic acid, and the resulting solution is then cooled as rapidly as possible to room temperature.

The mixture prepared in B is added to the solution prepared in A over a. period of 30-40 minutes, while stirring, and maintaining a temperature of 10-15 C. The resulting solution is stirred for about an additional 30 minutes, and one part of urea is added to remove excess nitrous acid.

The diazo solution thus prepared is added slowly to a cold water solution of sodium-q-sulfopropyl-p-hydroxypropylcresidine, and coupling is carried out as described in Example 8. When coupling is complete, the sodium salt oi. the azo compound is precipitated by the addition 01' sodium chloride, filtered and dried.

Example 10 38.1 parts of sodium-a-sulfobutyla'mylip methoxyl-a-naphthylamine are dissolved in water and coupled with the diazo solution-prepared as described in Example 9. The coupling may be eifected as described in Example 8. Upon the completion of coupling, the azo compound is precipitated, filtered and dried.

In the above examples, the azocompounds, except as noted, are isolated as the sodium salts. These can as well be isolated as the potassium salts by substituting potassium acetate for sodium acetate in the examples. The free sulfonic acid form of the azo compounds can be prepared by treating the sodium salts with hydrochloric acid and precipitating the resulting free acids by the addition of sodium chloride. The ammonium type salts of the so-prepared free acid forms of the azo compounds can be prepared by treating the free acid form with the appropriate ammonium base or salt, for exam-.

ple an ammonium hydroxide or an ammonium carbonate.

The foregoing examples illustrate the manner of preparation of the azo compounds of our invention, but it will be understood that the invention is not limited to the specific conditions described as various modifications within the scope of the invention can be made. For example, the acetic acid used in Examples 1, 2, 3,

4, 6 and 7 may be of varying strength and, while it is generally advantageous to use no more than is required for solution purposes, an excess may be employed. Similarly, another acid, such as hydrochloric acid, for example may be used in place of acetic acid.

Example 11 A. 20.8 parts of 2,6-dichloro-p-nitroaniline are dissolved in 231 parts of hot glacial aceticacid,

, minutes, while stirring, and maintaining a temperature of 10-15" C. Stirring is continued for one hour at room temperature, and then one part of urea is added to remove any excess nitrous acid.

20.8 parts of the sodium salt 01' cyclohexyl-vsulfopropylanilinecarom I l CHI-CHI Hz-CHr-CHz-BOaNa Example 12 29.3 parts of the sodium salt of methyltetrah ydrofuryl-p-sulfoethylanilink CHi CH: C I

N-C Hr-CH Ha I C Hr-C H:- S O 3N8 are dissolved in a-minimum amount of water and coupled in the usual manner with a diazo solution prepared by diazotizing 23.9 parts of 3-nitrofi-bromo-i-aminoacetophenone. When coupling is complete, the sodium salt of the azo compound formed is precipitated by the addition of sodium chloride, filtered, washed and dried.

Example 13 33.4 parts of the sodium salt of methylthiazolinyl y-sulfopropylaniline- I B--CH| Nc=N.c-cm

( 3H:-CHr-CH:S OsNa are dissolved in a minimum amount of water. The resulting solution is then cooled in any suitable manner to a temperature of 0-5 C. and coupled with a diazo solution prepared by diazocoupling is complete, the azo compound formed may be precipitated in the form of its sodium salt by the addition of sodium chloride. The salt may be recovered by filtering, after which it may be washed and dried.

Example is 21.7 parts of p-nitro-o-bromoaniline are added to 200 parts of water containing about 36 parts of 36% hydrochloric acid and a small amount of ice, and diazotized by addition oi 6.9 parts of sodium nitrite.

37.8 parts of p-bromophenyl-p-sulfoethylaniline- 0 0 cure Hg-SOzNfl 1 iHr-C Hr-SOgNa and dyes cellulose acetate rubine from an aqueous solution which may contain salt. I

Our invention will be further illustrated by the following tabulation, which gives the com position of a number of the water-soluble azo compounds of our invention, together with the color they produce on cellulose acetate, silk, or

tizing 26.4 parts of p-nitro-o-iodoaniline. when wool:

Amine Coupling Component 312L g-R &2

2methoxy-4-nitroaniline. Metllzyl-fl-sulfoethyl aniline sodium Red Begin"... Red.

53 i N-p-slmmm idiphenylaniine sod. salt. -..do .do Do.

ethyl-0s oethyl-a-naphtbylamine. Purple.-.. Purple.-.. Purple. 8- ulioethyl-a-naphtbyiaminc .do Do. Metllzylfi-sulfoethyl aniline sodium Red sa N-B-Sulioethyldiphenylamiuesod.salt. .-.do Do. Methyl-B-sulioethyl-a-naphthylamine. ...d Do. fi-Sulioetbyl-a-napbtbylamlne o --do Do. M c t lzyl-fi sulloethyl aniline sodium Orang Orange.... Orange N-B-Bulioethyldiphenylaminsod.salt. do -.-d0 Do. Methyl-g-sulioethyl-a-naphthylamine. omrigge- Orangeofigere fisulfoethyl-wnaphthylamine ...do o Do. Motleylfi-suliodthyl aniline sodium Yellow. Yellow..-. Yellow N-p-flulfoethyldiphenylamine sod. salt. do -..do Do. Metbyl-dsulfoethyl-a-naphthylamine Orange--. Orange Orange fi-sulicethyi-a-naphthylamine ...do ..do-.... Do. .-Metbyl-p suifoothyl aniline sodium Oran Orange- Oran sal ye ow yellow ye ow N-fi-Sulioethyldiphenylaminesodsalt. d Do. Methyl-fisulfoethyl-a-naphthylamine'. B-Sulfoetbylwnaphthylamlne Metllzylb-sulioetbyl aniline sodium sa N-B-sulioeth ldl henylamine sod. salt Do. Metbyl-p-su yl'a-naphthylamm e. 0%goorrgnage- 0%ge- Dom.-. fi-Sulfoetbylu-naphthylamine ..--.rm-' Do: p-Chlmo-o-nitroaniline Metlizyl-fl-sulloethyl aniline sodium Orange.... Orange....

1 so v Do N-a-sulioethyldighenylamine sod. salt -do....-.. ...do Do. I Mcthyl-fi-sulioet yl-u naphtbylamine. ge- Oranizad e- Oransmd ol v r D0 fl-Sulloethyl-a-napthylamine do D0. p-Aminoacatophenone.. Methyl-dsulfoetbyl aniline sodium Orange.... Orange.... Orange.

N-fi-su lioethyldi lilhenylamine sod. salt m n n Do. Do Modiyl-fi-sulloot ylu-naphtbylamine. Orange- Orange- Orange- Do min :in Do,

' It will be noted that, as the azo compounds of our invention are water soluble, they are suitable for the direct coloration of organic derivatives of cellulose, silk and wool, or. mixtures of these ma terials. The dyeing operationswill be conducted in accordance with the usual dyeing practice, salt being added, if desired, to facilitate exhaustion, of the dye bath. Dyeing can be carried out as follows:

' Example 15 2.5 parts (by weight) of the dye prepared by diazotizing 2-.methoxy-4-nitroaniline and'coupling it with methyl-prsulioethylaniline sodium saltare dissolved in 230 parts of water and the mixture heated to about 80-85 C. and maintained at this temperature throughout the dyeing operation. 100 parts of cellulose acetate (1. e., acetate silk) are added and allowed to remain in thedye bath, salt being added as desired to promote exhaustion of the dye bath, until dyeing is complete, after which the silk is removed, washed with soap,

rinsed anddried. The cellulose acetate is dyed a red color.

Silk or wool or mixtures of either or both of these with organic derivatives of cellulose,

cellulose acetate, for example, may be substituted for cellulose acetate in the foregoing example, and similarly dyed. In general about -2.5 parts of dye per 100 parts of the material to be dyed will be used, but this proportion is subject to variation, as are the amount of water and temperature at which the dyeing operation is conducted. The amount of salt added will vary with different dyes of this series and the depth of shade required, but in'general it will vary between 10 and 50 per cent of the weight of the cloth being dye'd,

although greater or lesser amounts may be used I it desired.

It will be understood that the. examples given are intended to be illustrative and not limiting of pared and how they may be used for dyeing as theseare subject to modification,

- Color on Color on Color on Amine Coupling Component Acetate. silk w 001 'Mel l yl-B-sulloethyl aniline sodium Orange.... Orange.... Oran ge.

sa N-B-sulloethyldlphenylnminesodml do do Do. Methyl-fi-sulfoetbyl-a-naphthylnmine. Red Red Red. B-Sulloethyl-a-nnphthylaminn (in do D Metllzyl-fi-sulfoethyl aniline sodium Red Red Red. N -B-sulfoetbyldipbenylnminesod.sel do do Do. Methyl-fi-sulioethyl-a-nnphthylnmine. Reddish- Reddish- Reddishblue. blue. blue. fi-Sultoethyl-a-napbthylamine do d Do.

Meliltiyl-fl-sulioethyl aniline sodium d Red Red.

so N-fi-sulloeth ldighenylaminemd. salt do d Do. Methyl-fi-su loet yl-wnaphthylnmina Blue- Blue- Bluegreen. green. green. 8' sulfoethyl-a-naphthylnmine do do Do. Melilgyl-fl-sulfoetbyl aniline sodium Red. 'Red Red.

sa N-B-sulfoethyldiphenylamine sod. salt. do do Do. Methyl-fl-sulioethylu-naphthylamine. Blue Blue Blue. fl-Sulloethyl-a-na lithylamine ..do 0...... Do. Ammonlum-y-su lopropyl-butyl-m- Rubine.-- Rubine.-- Rubine. A h ch l oroaniline. o O o rn "n gnnno n Q-dinitmnni inn do F gi P12 1351," Pa g}; 2,4-dinitro-e bromoanihne nn Sodium -sulfopropyl-fl-hydroxy- Re dish Reddlsh- Reddlslipropylcresidine. blue. .blue. blue. 2, 4-6- trinitroanihne dov Blue Blue Blue. 2,4-dm1tro-6-haloaniline, Sodium-d-sulfobutylamyl(B-alkoxyor do (in D alkyl or halo)-a-napbthylnmine. lfi-dmitro-fl-carbethoxy enido do do Do. e.

' Do Sodium -sulfopropylbutyl-u-nephdo do Do.

' hylnmines What we claim as our invention and desire to secure by Letters Patent of the United States is:

1. A compound consisting of a nuclear non-sulfonated aryl nucleus linked to a second nuclear non-sulfonated aryl nucleus by an azo group, the compound containing as a nuclear substituent at least one group oi. the following structure:

' s-soiz wherein A represents an alkylene group other than amethylene group, X represents hydrogen,

an alkyl, a cycloalkyl, a nuclear non-sulfonated aryl or a nuclear non-sulfonated heterocyclic group and Z represents hydrogen, an alkali-forming metal or an ammonium radical.

2. The water-soluble salts of the 9.20 compounds represented by the general formula:

. x wherein R and B. represent nuclear non-sulfonated aryl nuclei, A represents an alkylene group other than methylene, X represents hydrogen, an

alkyl group, a. cycloalkyl group, a nuclear nonsulfonated heterocyclic group or a nuclear nonsuli'onated aryl group and Z represents hydrogen,

an alkali-forming metal or an ammonium radical. 4. The process of coloring cellulose acetate which comprises efiectingcoloration by applying thereto an azo dye having the general formula:

A-soiz R-N=NR'N x wherein R and R represent nuclear non-sulfonated aryl nuclei, A represents an alkylene group other than methylene, X represents hydrogen, an alkyl group, a cycloallryl group, a nuclear non-sulfonated heterocyclic group or a nuclear nonsulfonated aryl group and Z represents hydrogen, an alkali-forming metal or an ammonium radical.

5. A process for coloring mixed fabrics comprising organic derivatives of cellulose and a material selected from the group consisting of silk and wool which comprises effecting coloration by applying thereto an azo dye having the general formula:

wherein R. and R represent nuclear non-sulfonated aryl nuclei, A represents an alkylene group other than methylene, X represents hydrogen, an alkyl group, a cycloalkyl group, a. nuclear nonsulfonated heterocyclic group or a nuclear nonsulfonated aryl group and Z represents hydrogen, an alkali-forming metal or an ammonium radical.

6. A process of preparing azo compounds which comprises coupling a diazotized aromatic amine of the benzene or naphthalene series with an aryl nucleus of the benzene or naphthalene series containing as a nuclear substituent a group of the following structure:

A-SOsZ wherein A represents an alkylene group other than methylene, X represents hydrogen, an alkyl group, a cycloalkyl group, a nuclear non-sulfonated heterocyclic group or a nuclear non-sulfonated aryl group and Z represents hydrogen, an alkali-forming metal or an ammonium radical.

'7. The water-soluble salts of the azo compounds represented by the general formula:

wherein R and R each represents a nuclear nonsulfonated aryl nucleus of the benzene series, A represents an alkylene group other then methylene and X represents a member selected from the class consisting of hydrogen, an alkyl group, a cycloalkyl group, a. nuclear non-sultonated heterocyclic group and a nuclear non-sulionated aryl group. o.

8. The water-soluble azo compounds represented by the general formula:

wherein R and R. each represents a nuclear non-sulfonated aryl nucleus, A represents an alkylene group other than methylene, X represents a member selected from the class consisting of hydrogen, an alkyl group, a cycloa'lkyl group, a. nuclear non-sulfonated aryl group and arouses wherein R and R each represents a nuclear non-sulfonated aryl nucleus of the benzene series, A represents an alkylene group other than methylene, X represents a member selected from the class consisting of hydrogen, an alkyl group, a cycloalkyl group, a nuclear non-sulfonated heterocyclic group and a nuclear non-sulfonated aryl nucleus of the benzene series, and Z represents a member selected from the class consisting of hydrogen, an alkali-forming metal and.

an ammonium radical.

10. The process of coloring cellulose acetate which comprises efiecting coloration by applying thereto an azodye having the general formula:

wherein R and R each represents a nuclear non-sulfonated aryl nucleus of the benzene series, A represents an alkylene group other than methylene, X represents a member selected from the class consisting of hydrogen, an alkyl group, a cycloalkyl group, a nuclear non-sulfonated heterocyclic group and a nuclear non-sulfonated aryl nucleus of the benzene series and Z represents a member selected from the class consisting of hydrogen, an alkali-forming metal and an ammonium. radical.

11. The process of coloring a cellulose acetate which comprises effecting coloration by applying thereto on azo dye having the general formula:

wherein R and R each represents a nuclear non-sulfonated aryl nucleus of the benzene series, A represents an allrylene group other than methylene, X represents a member selected from 1 the class consisting of hydrogen, an aliryl group,

a, cycloalkyl group, a nuclear non-sulfonated heterocyclic group and a nuclear non-sulfonated aryl nucleus of the benzene series. and Z repre-' sents a member selected from the class consisting of hydrogen, an alkali-forming metal and an ammonium radical.

12. The process for coloring mixed fabrics comprising organic derivatives of cellulose and a material selected from the group consisting of silk and wool which comprises eflecting coloration by applying thereto an azo dye having the general formula:

A-smz n- =NR' wherein R and R' each represents a nuclear non-sulfonated aryl nucleus of the benzene or naphthalene series, A represents an alkylene iii 1o sented by the general formula:

group other than methylene, X represents a member selected from the class consisting of hydrogen, an alkyl group, a cyclo alkyl group, a nuclear non-sulfonated heterocyclic group and a nuclear non-sulfonated aryl nucleus of the benzene or naphthalene 'series and Z represents hydrogen, an alkali-forming metal or an ammonium radical.

13. The water soluble azo compounds r epre- 15 wherein R and R each represents a nuclear gen, an alkali-forming metal or an ammonium radical.

14. The water soluble azo compounds rep sented by the general formula:

wherein R represents a nuclear non-sulfonated aryl nucleus of the benzene series containing no nitro group, R represents a nuclear non-sulfonated aryl nucleus of the benzene series, A represents an alkylene group other than methylene, X represents a member selected from the class consisting of hydrogen, an alkyl group, a cycloalkyl group, a nuclear non-sulfonated heterocyclic group and a. nuclear non-sulfonated aryl nucleus of the benzene series and Z represents hydrogen, an alkali-forming metal or an ammonium radical.

JAMES G. McNALLY.

JOSEPH B. DICKEYV 

